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Transcriptional regulation underlies most developmental programs and physiological responses to environmental changes in plants. Transcription factors (TFs) play a key role in the regulation of gene expression by binding specifically to short DNA sequences in the regulatory regions of genes: the TF binding sites (TFBSs). In recent years, several bioinformatic tools have been developed to detect TFBSs in candidate genes, either by de novo prediction or by directly mapping experimentally known TFBSs. However, most of these tools contain information for only a few species or require multi-step procedures, and are not always intuitive for non-experienced researchers. Here we present TFBS-Discovery Tool Hub (TDTHub), a web server for quick and intuitive studies of transcriptional regulation in plants. TDTHub uses pre-computed TFBSs in 40 plant species and allows the choice of two mapping algorithms, providing a higher versatility. Besides the main TFBS enrichment tool, TDTHub includes additional tools to assist in the analysis and visualization of data. In order to demonstrate the effectiveness of TDTHub, we analyzed the transcriptional regulation of the anthocyanin biosynthesis pathway. We also analyzed the transcriptional cascades in response to jasmonate and wounding in Arabidopsis and tomato (Solanum lycopersicum), respectively. In these studies, TDTHub helped to verify the most relevant TF nodes and to propose new ones with a prominent role in these pathways. TDTHub is available at http://acrab.cnb.csic.es/TDTHub/, and it will be periodically upgraded and expanded for new species and gene annotations.

The objective of this study was to build an understanding and optimize the secondary drying step of a freeze-drying process using a drug formulation from Fresenius Kabi (FK1) as a case study. For t...

The application of quality by design (QbD) is becoming an integral part of the formulation and process development for pharmaceutical products. An essential feature of the QbD philosophy is the design space. In this sense, a new approach to construct a process design space (PDS) for the primary drying section of a freeze-drying process is addressed in this paper. An effective customized design of experiments (DoE) is developed for freeze-drying experiments. The results obtained from the DoE are then used to construct the product-based PDS. The proposed product-based PDS construction approach has several advantages, including (1) eliminating assumptions on the heat transfer coefficient and dried product resistance, as it is constructed from experimental results specifically obtained from a given formulation, yielding more realistic and reliable results and (2) PDS construction based on a narrow range of product temperatures and considering the variations in product temperature and sublimation rate of vials across a shelf. This guarantees the effectiveness and robustness of the process and facilitates the process scale-up and transfer. The PDS developed herein was experimentally verified. The PDS predicted parameters were in excellent agreement with the experimentally obtained parameters.

Plant growth and adaptation to environmental fluctuations involve a tight control of cellular processes which, to a great extent, are mediated by changes at the transcriptional level. This regulation is exerted by transcription factors (TFs), a group of regulatory proteins that control gene expression by directly binding to the gene promoter regions via their cognate TF-binding sites (TFBS). The nature of TFBS defines the pattern of expression of the various plant loci, the precise combinatorial assembly of these elements being key in conferring plant's adaptation ability and in domestication. As such, TFs are main potential targets for biotechnological interventions, prompting in the last decade notable protein-DNA interaction efforts toward definition of their TFBS. Distinct methods based on in vivo or in vitro approaches defined the TFBS for many TFs, mainly in Arabidopsis, but comprehensive information on the transcriptional networks for many regulators is still lacking, especially in crops. In this chapter, detailed protocols for DAP-seq studies to unbiased identification of TFBS in potato are provided. This methodology relies on the affinity purification of genomic DNA-protein complexes in vitro, and high-throughput sequencing of the eluted DNA fragments. DAP-seq outperforms other in vitro DNA-motif definition strategies, such as protein-binding microarrays and SELEX-seq, since the protein of interest is directly bound to the genomic DNA extracted from plants yielding all the potential sites bound by the TF in the genome. Actually, data generated from DAP-seq experiments are highly similar to those out of ChIP-seq methods, but are generated much faster. We also provide a standard procedure to the analysis of the DAP-seq data, addressed to non-experienced users, that involves two consecutive steps: (1) processing of raw data (trimming, filtering, and read alignment) and (2) peak calling and identification of enriched motifs. This method allows identification of the binding profiles of dozens of TFs in crops, in a timely manner.

We examined the rheological and tribological behavior of novel formulations based on castor oil and epoxidized cellulose pulp intended for use as biodegradable lubricating greases. Epoxidized cellulose pulp was found to thicken castor oil to a variable extent depending on its modification degree and the epoxide compound. Greases were subjected to small-amplitude oscillatory shear tests, evaluating the temperature-dependence of the plateau modulus. In addition, friction coefficient and wear were determined in a steel–steel ball-on-three-plates tribological configuration, at two different temperatures (25 and 95 °C), generally obtaining smaller values of both parameters when using aromatic diepoxides instead of aliphatic to modify the cellulose pulp.

Nowadays, there is a marked tendency in order to develop new composite fibers based on proteins and polysaccharides due to these materials can exhibit a wide range of tailored functional properties. In this framework, this study has been focused on the development of novel potato protein (PP)-based composite fibers by electrospinning technique using formic acid as solvent media. At the selected electrospinning conditions, PP pure solutions (3–8 wt.%) showed inadequate spinnability. Interestingly, the addition of polyethylene oxide (PEO) as co-blending polymer improved the solutions viscoelasticity and hence, the solutions spinnability. Composite fibers with enhanced properties were obtained at higher PEO concentrations while systems with higher PP protein contents led to electrosprayed separate aggregates of particles. Fourier-transformed infrared spectroscopy and thermogravimetric analysis results showed that the obtained composite fibers were composed of both PP and PEO materials. DSC results show that PP influences on PEO polymer thermal behaviour lowering its melting point, and an increase of the PEO amount produces a decrease of the α-helix denaturation temperature. Due to the properties of PP and PEO, these novel composite fibers could find importance in a diverse range of applications as advanced functional materials in fields like food science and biomedical applications.

To obtain multiple emulsions containing Agnique™ AE 3-2H as oil phase and Atlas™ G-5000 as emulsifier, two formulation variables were studied: the effect of the Atlas™ G-5000 concentration in emulsions containing 15 wt% Agnique™ AE 3-2H and the study of the influence of the solvent concentration maintaining the Agnique™ AE 3-2H/Atlas™ G-5000 ratio equal to 10. To assess microstructure and physical stability of these emulsions different techniques were employed, namely laser diffraction, transmitted light optical microscopy, steady-state measurements, and multiple light scattering. An increase in copolymer concentration and solvent concentration provoked a decrease in Sauter diameter but an increase in volume mean diameter and polydispersion due to droplet coalescence. Regardless of polymer concentration, all emulsions showed Newtonian behavior which led to shear thinning with increasing oil concentration. The main destabilization processes are creaming, when the concentration of polymer or solvent is low, and coalescence, when both concentrations are high.

The overall objective of this work was to study the combined effect of hydrogen peroxide (H2O2) and light emitting diodes (LED) process assisted by titanium dioxide (TiO2) on the photo-oxidation behaviour of polylactic acid (PLA). The photochemical behaviour of PLA in a TiO2 suspensions was studied by irradiation under photo-oxidative conditions (λ > 454 nm, ambient temperature and with or without the presence of H2O2). The chemical and thermal properties induced by LED irradiation process were analyzed using fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H NMR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). It was found that the presence of photoactive TiO2 particles, combined with H2O2 leads to strong impact on the physicochemical properties of the samples during photochemical ageing. A new comprehensive mechanism for the photo-oxidation of PLA for these conditions was discussed.

This paper presents the rheological properties of three types of lime putty, specifying the influence of their origin. The study aims to compare a special lime putty prepared from phosphogypsum with a commercial lime powder and an aged lime putty. The results obtained in terms of chemical composition, crystalline structure, grain size and rheological characterization, (linear viscoelasticity, shear rate and time-dependent flow behaviour) are presented in the study. Putties studied present a similar rheological response, which mainly depends on the particle size and water content. Lower values of the linear viscoelastic functions and viscosity were found for the phosphogypsum lime putty, in agreement with the higher particle size. Transient flow tests reveal a predominant elastic response with no significant shear-induced structural perturbations. However, either a thickening phenomenon over time, i.e. rheopexy, favoured at low shear rates, or a viscosity decrease, i.e. thixotropy, favoured at high shear rates, was observed., The authors would like to thank the aid of CITIUS at the University of Seville for the use of their laboratories for the characterization analyses. A.M.B.-L. has received a Ph.D. Research Grant from the Ministerio de Education, Cultura y Deporte (FPU16/03697).

A geothermal power development project begins with a preliminary study of the region of interest. This is followed by a smaller area exploration stage in which geoscientific studies are performed. A geothermal system conceptual model is constructed before proceeding to the prefeasibility stage, where data analysis and risk assessment are carried out prior to recommending drilling wells. The feasibility stage of a geothermal project is described in this chapter, the aim of which is making the project viable and facilitating its financing. From production tests, field expansion plans are designed for drilling new producer wells. The tasks contained in the feasibility stage of a general project are reviewed. Different types of geothermal power generation plants are examined. Options available to developers include (1) dry steam plants using direct flow steam, (2) flash steam plants using a mixture of liquid water and steam, and (3) binary cycle plants. A cooling system is required to operate any power plant.

Freeze-drying, a drying unit operation frequently used in food, pharmaceutical, and biopharmaceutical industries to prolong the shelf life of labile products, is an energy-intensive, time-consuming, and expensive process. Although all three steps (freezing, primary drying, and secondary drying) of freeze-drying are important, primary drying is the longest and most critical one. As sublimation during primary drying is mainly described in terms of heat and mass transfer, the present work provides extensive theoretical and experimental analyses of these processes. First, a detailed review of the current state-of-the art of freeze-drying, focusing on the drying stage, is given, which contributes to a fundamental understanding of the drying process. Second, a detailed experimental study of the drying section of the freeze-drying process is discussed, furnishing information on the relationship between input and output process parameters during the primary drying stage and thus aiding freeze-drying process design and optimization. In this regard, the influence of primary drying input parameters (i.e., shelf temperature and chamber pressure) and vial position on output parameters such as product temperature, sublimation rate, overall vial heat transfer coefficient, and resistance to mass transfer of the dried product are extensively discussed. For all combinations of shelf temperature and chamber pressure studied herein, the highest product temperature, sublimation rate, and overall vial heat transfer coefficient are observed in front edge vials, whereas the lowest values are observed in center vials. In general, the highest sublimation rate, at a given product temperature, is observed for low chamber pressure-high shelf temperature combinations.

This study explores the suitability of residual lignin-containing fractions generated as side-streams in different conversion processes of eucalypt and pine woods as thickening agents in bio-lubricant formulations. These conversion processes included fermentable sugars extraction by autohydrolysis or steam explosion and kraft pulping. Structural properties of lignin fractions were characterized by FTIR, 1H and 13C NMR, two-dimensional NMR, TGA and SEC, whereas their compositions were analysed by standard analytical methods. On the other hand, chemical oleogels were prepared with NCO-functionalized residual lignin fractions, and characterized by means of rheological, tribological and AFM techniques. Hydrolysis lignin fractions exhibited a great content of carbohydrates, especially glucose (46.0-48.5%), xylose (4.3-15.6%) and lignin (32.5-39.9%) with a well-maintained structure, displaying the main inter-unit linkages and low phenolic content. By contrast, kraft lignin fractions presented a lower carbohydrate content, mainly xylose (3.4-4.3%), and higher content (44.9-67%) of severely degraded lignin, showing a dramatic reduction of inter-unit linkages, and thereby high phenolic content. The rheological response of NCO-functionalized lignin fractions-based oleogels is highly influenced by the composition and chemical structure of residual lignin fractions. Moreover, these oleogels presented suitable tribological properties with values of the friction coefficient lower than those typically exhibited by standard lubricating greases.

There is a growing concern about chronic diseases such as obesity, diabetes, hypertension, hypercholesterolemia, cancer and cardiovascular diseases resulting from profound changes in the western lifestyle. Aquaculture by-products are generated in large quantities and they can be profitably recycled through their bioactive compounds used for health or food supplements. Improving waste utilization in the field of aquaculture is essential for a sustainable industry to prevent or minimize the environmental impact. In this sense fish by-products are a great source of protein and omega-3 polyunsaturated fatty acids which are particularly studied on Atlantic salmon or rainbow trout. Fish protein hydrolysate (FPH) obtained from chemical, enzymatical and microbial hydrolysis of processing by-products are being used as a source of amino acids and peptides with high digestibility, fast absorption and important biological activities. Omega-3 polyunsaturated fatty acids, eicosapentaenoic (EPA) and docosahexaenoic (DHA) from fish discards have been reported to decrease postprandial triacylglycerol levels, reduction of blood pressure, platelet aggregation and the inflammatory response. Crustacean by-products can also be used to produce chitosan with antioxidant and antimicrobial activity for food and pharmaceutical industries and carotenoids with important biological activity. Seaweeds are rich in bioactive compounds such as alginate, carrageenan, agar, carotenoids and polyphenols with different biological activities such as antioxidant, anticancer, antidiabetic, antimicrobial or anti-inflammatory activity. Finally, regarding harvest microalgae, during the past decades, they were mainly used in the healthy food market, with75% of the annual microalgal biomass production, used for the manufacture of powders, tablets, capsules or pills. We will report and discuss the present and future role of aquaculture by-products as sources of biomolecules for the design and development of functional foods/beverages. This chapter will focus on the main bioactive compounds from aquaculture by-products as functional compounds in food and their applications in biomedicine for the prevention and treatment of diseases.

There is a growing concern about chronic diseases such as obesity, diabetes, hypertension, hypercholesterolemia, cancer and cardiovascular diseases resulting from profound changes in the western lifestyle. Aquaculture by-products are generated in large quantities and they can be profitably recycled through their bioactive compounds used for health or food supplements. Improving waste utilization in the field of aquaculture is essential for a sustainable industry to prevent or minimize the environmental impact. In this sense fish by-products are a great source of protein and omega-3 polyunsaturated fatty acids which are particularly studied on Atlantic salmon or rainbow trout. Fish protein hydrolysate (FPH) obtained from chemical, enzymatical and microbial hydrolysis of processing by-products are being used as a source of amino acids and peptides with high digestibility, fast absorption and important biological activities. Omega-3 polyunsaturated fatty acids, eicosapentaenoic (EPA) and docosahexaenoic (DHA) from fish discards have been reported to decrease postprandial triacylglycerol levels, reduction of blood pressure, platelet aggregation and the inflammatory response. Crustacean by-products can also be used to produce chitosan with antioxidant and antimicrobial activity for food and pharmaceutical industries and carotenoids with important biological activity. Seaweeds are rich in bioactive compounds such as alginate, carrageenan, agar, carotenoids and polyphenols with different biological activities such as antioxidant, anticancer, antidiabetic, antimicrobial or anti-inflammatory activity. Finally, regarding harvest microalgae, during the past decades, they were mainly used in the healthy food market, with > 75% of the annual microalgal biomass production, used for the manufacture of powders, tablets, capsules or pills. We will report and discuss the present and future role of aquaculture by-products as sources of biomolecules for the design and development of functional foods/beverages. This chapter will focus on the main bioactive compounds from aquaculture by-products as functional compounds in food and their applications in biomedicine for the prevention and treatment of diseases.

Freeze-drying, a drying unit operation frequently used in food, pharmaceutical, and biopharmaceutical industries to prolong the shelf life of labile products, is an energy-intensive, time-consuming, and expensive process. Although all three steps (freezing, primary drying, and secondary drying) of freeze-drying are important, primary drying is the longest and most critical one. As sublimation during primary drying is mainly described in terms of heat and mass transfer, the present work provides extensive theoretical and experimental analyses of these processes. First, a detailed review of the current state-of-the art of freeze-drying, focusing on the drying stage, is given, which contributes to a fundamental understanding of the drying process. Second, a detailed experimental study of the drying section of the freeze-drying process is discussed, furnishing information on the relationship between input and output process parameters during the primary drying stage and thus aiding freeze-drying process design and optimization. In this regard, the influence of primary drying input parameters (i.e., shelf temperature and chamber pressure) and vial position on output parameters such as product temperature, sublimation rate, overall vial heat transfer coefficient, and resistance to mass transfer of the dried product are extensively discussed. For all combinations of shelf temperature and chamber pressure studied herein, the highest product temperature, sublimation rate, and overall vial heat transfer coefficient are observed in front edge vials, whereas the lowest values are observed in center vials. In general, the highest sublimation rate, at a given product temperature, is observed for low chamber pressure-high shelf temperature combinations.

A method to prepare solvent free castor oil (CO) based polyurethane (PU) adhesives with different ratios of CO and hexamethylene diisocyanate (HMDI) has been developed and the relationships between the microstructure and mechanical properties investigated. Solvent free castor oil-based PU adhesives were synthesized by promoting the reaction between castor oil and HMDI, at room conditions, and by varying the CO/HMDI weight ratio in the range 1:0.032–1:0.32 wt%. The curing of these adhesives did not require any external stimuli such as heat or irradiation treatment and once cured at room temperature they were stable up to 140 °C and water-resistant. A multi-technique approach was used to characterize so-obtained adhesives. The adhesion energy in metal–metal contact was evaluated as a function of the debonding velocity (Vd) through tack experiments. The mechanical properties were influenced by the NCO/ OH ratio, which varies the crosslinking density in the adhesives. Moreover, the structure–mechanical property relationship was explored and the inter-correlation between the storage modulus (G’), adhesion energy (Ead) and correlation length (ξ) detailed, with both G’, Ead increasing while ξ decreased. These solvent-free bio-based adhesives showed capability to adhere different substrates such as wood, paper, textile, and metal, which makes them promising candidates in different industrial and commercial applications.

The main aim of this study was to elucidate the influence of an alkali treatment on the rheological and tribological properties, and microstructure, of cellulose pulp-based gel-like dispersions potentially usable as biodegradable lubricating greases. For this purpose, cellulose pulp was treated with sodium hydroxide under different conditions of alkali concentration (20, 30 and 40%), temperature (20, 45 and 75 °C) and contact time (1 and 2 h). Favourable conditions relative to the rheological response of a commercial lithium lubricating grease used as benchmark were found to be 40% NaOH, 20 °C and 2 h. Gel-like dispersions with acceptable lubrication properties in terms of consistency indices, mechanical stability, and frictional and wear performance, were obtained by using a 6–7% (w/w) proportion of cellulose pulp.

We present herein an unexpected selectivity in the reactions of castor oil with 1,6-hexamethylene diisocyanate (HMDI) in the absence of catalysts, heat or N2 protection to give monofunctionalized castor oil derivatives. The reagents were stirred at room temperature for 24 h, and the resulting formulations characterized with infrared spectroscopy, thermogravimetric analysis and NMR. In the highly viscous neat systems, the reaction stops at the formation of NCO-terminated urethane monomers. When the mass transfer limitations due to high viscosity are minimized, the NCO-terminated urethane monomers go on to form not di- or tri- urethane monomers, but cross-linked monourethane dimers. We propose that the selectivity of the functionalization reaction of castor oil originates from a hydrogen bonding mediated steric hindrance on two out of the three fatty acid moieties. This selectivity is normally associated with conformational preferences in crystallized triglycerides, and indicates an inherent level of struct...

This work advances the development and use of sustainable polyurethane elastomers as green adhesives by providing insights into the mechanisms of humidity-induced changes on adhesive performance. Using a model adhesive prepared from equimolar ratios of castor oil and hexamethylene diisocyanate under facile reaction conditions, we show that the subtle changes in the chemical composition which occur with curing under different humidity environments significantly impact the cohesive integrity of the adhesives and, thus, their performances with different substrates. The curing chemistry was evaluated based on the isocyanate consumption, which was followed using Fourier Transform Infrared Spectroscopy and Differential Scanning Calorimetry. Thermal, mechanical and adhesion properties were evaluated from thermogravimetric analysis, differential scanning calorimetry, rheology, tacking and lap shear tests. Moisture-cured adhesives were less covalently crosslinked, harder, more resistant to deformation, and recovered faster upon shear deformation compared to those cured otherwise. These mechanical properties complimented adhesive lap shear performance with substrates which formed covalent bonds during curing. For substrates with which covalent bonds could not form during curing, however, decreased internal cohesive integrity and associated increased hardness by urea formation resulted in poorer adhesive lap shear performance. This is contrary better tack performances obtained for the moisture-cured adhesives, attributed to their increased polarity and the energy dissipating ability.

This work describes the solid-state fermentation(SSF) of wheat straw with Streptomyces sp. MDG147 and further soda-pulping process to obtain wheat straw soda lignins(WSLs). Subsequently, these WSLs were NCO-functionalized with 1,6-hexamethylene diisocyanate and then dispersed in castor oil to achieve stable oleogels. The WSLs were characterized using standard analytical methods, gel permeation chromatography, Fourier transform infrared spectroscopy,differential scanning calorimetry, and thermogravimetric analysis. Rheological properties of oleogels were determinedby means of small-amplitude oscillatory shear and viscous flow measurements. The enzymatic profile and production oflignin−carbohydrate complexes were recorded along the growth time of Streptomyces, whose life cycle was achieved after 7 days. NCO-functionalized WSL was able to chemically interact with castor oil via urethane bonding, providing oleogels with suitable rheological characteristics. Linear viscoelastic functions and viscosity values of oleogels were higher when wheat straw was submitted to SSF using Streptomyces, turning out in stronger oleogels., Ministerio de Economía, Industria y Competitividad

On account of the heavy reliance of the adhesive industry on petrochemical derivatives, there is a particular interest in the development of bio-sourced polyurethane adhesives. In this context, a moisture-curable polyurethane adhesive has been synthesized from cellulose acetate and castor oil, using 1,6-hexamethylene diisocyanate as a crosslinker. In particular, this research delves into the rheological and adhesion properties achieved by bio-inspired polyurethanes cured at 20 °C and under different relative humidity conditions (11, 33, 64, and 90.4%). Green shear and peeling strengths on wood and stainless steel as well as chemical structure variations were monitored over curing time. Moreover, fully cured polyurethane-urea adhesives were thermally (thermogravimetric and differential scanning calorimetric analyses) and rheologically characterized within the linear viscoelastic region. The results corroborated the noteworthy impact of environmental humidity throughout the curing process of the synthesized bio-sourced adhesives, favoring the formation of urea linkages, while sharply reducing the crystalline/amorphous ratio. All the bio-based polyurethane-urea copolymers showed a predominant elastic behavior and the time-Temperature superposition principle was found to be applicable up to around 120 °C, due to the thermal rearrangement of the hard segment units. The crosslinking density of the resulting supramolecular structure depends on the humidity-driven balance between the urethane and urea linkages production. As a consequence of the balance between the establishment of bidentate hydrogen bonds and the curing rate, moisture curable polyurethane adhesive cured at 33% relative humidity exhibited the most appropriate shear adhesion performance on wood, while the debonding shear strength on stainless steel increased with the relative humidity due to the higher urea:urethane ratio and larger proportions of non-bonded urethane and urea groups, thus enhancing secondary interactions. Therefore, on the basis of the present study results, it might be concluded that the synthesis of bio-inspired moisture-curable polyurethane can be tuned according to its end-use application through the control of the environmental conditions, and thereby optimizing their adhesion performance, while meeting the Green Chemistry tenets.

8 Pág. Instituto de Ciencias Forestales (ICIFOR), In this study, modified residual lignins from barley and wheat straws submitted to solid-state fermentation with diverse Streptomyces strains were targeted as binders in eco-friendly castor oil-based polyurethane adhesive formulations. The thermo-rheological and adhesion properties of these adhesives were examined and related to the solid-state fermentation yields. Viscoelastic properties were enhanced by lignin addition, and the Streptomyces action generally increased the values of the linear viscoelastic functions. Adhesion performance was dominated by lignin source and further Streptomyces activity and can be correlated with the resulting lignocellulosic composition. Wheat straw lignin-based polyurethane adhesives showed the best performance in metal-textile peeling tests, whereas barley straw lignin provided the best achievements in terms of shear strength in metal-metal and wood-wood joints. Overall, solid-state fermentation with Streptomyces demonstrated to be a suitable pretreatment to conveniently modify and improve residual lignin fractions for application as binders in environmental-friendly polyurethane adhesive formulations., This work was partially funded by two coordinated research MINECO-ERDF projects (CTQ2014-56038-C3-1R and CTQ2014-56038-C3-2R) and the ERDF-Junta de Andalucía 2014-2020 Operational Programme (project UHU-1252599). A.M.B-L. has received a Ph.D. Research Grant from the Ministerio de Educación, Cultura y Deporte (FPU16/03697). The authors gratefully acknowledge the financial support.

The present work focuses on the development of lignin micro- and nano-structures obtained by means of electrohydrodynamic techniques aimed to be potentially applicable as thickening or structuring agents in vegetable oils. The micro- and nano-structures used were mainly composed of eucalyptus kraft lignin (EKL), which were doped to some extent with polyvinylpyrrolidone (PVP). EKL/PVP solutions were prepared at different concentrations (10–40 wt.%) and EKL:PVP ratios (95:5–100:0) in N, N-dimethylformamide (DMF) and further physico-chemically and rheologically characterized. Electrosprayed micro-sized particles were obtained from solutions with low EKL/PVP concentrations (10 and 20 wt.%) and/or high EKL:PVP ratios, whereas beaded nanofiber mats were produced by increasing the solution concentration and/or decreasing EKL:PVP ratio, as a consequence of improved extensional viscoelastic properties. EKL/PVP electrospun nanofibers were able to form oleogels by simply dispersing them into castor oil at nanofiber concentrations higher than 15 wt.%. The rheological properties of these oleogels were assessed by means of small-amplitude oscillatory shear (SAOS) and viscous flow tests. The values of SAOS functions and viscosity depended on both the nanofiber concentration and the morphology of nanofiber templates and resemble those exhibited by commercial lubricating greases made from traditional metallic soaps and mineral oils, This work is part of a research project (Ref. RTI2018-096080-B-C21) sponsored by the MICINN-FEDER I+D+i Spanish Programme. The authors gratefully acknowledge their financial support. J.F.R.-V. acknowledges receiving the Ph.D. Research Grant PRE2019-090632 from MICINN (Spain)

In this work, alkali lignin together with different diisocyanates (hexamethylene diisocyanate (HDI), isophorone diisocyanate (IDI), toluene diisocyanate (TDI) and 4,4′-methylenebis (phenyl isocyanate) (MDI)) have been tested as gelling agents in a castor oil medium. A two-step process comprising first lignin functionalization with a diisocyanate and then the formation of a bio-based polyurethane with gel-like characteristics by combining the functionalized lignin with castor was followed. FTIR and thermogravimetry analysis were carried out on both the gelling agents and resulting oleogels. Moreover, oleogel rheological properties were evaluated by means of small-amplitude oscillatory shear (SAOS) tests and viscous flow measurements. The influences of time-temperature processing conditions during oleogel formation, lignin/diisocyanate ratio and functionalized lignin concentration on the rheological properties of oleogels were analyzed using HDI as crosslinker. 30% (w/w) thickener concentration and room temperature processing were selected to prepare oleogels with the rest of diisocyanates considered. Under the same conditions, HDI-functionalized lignin-based oleogels showed the strongest gel-like behavior whereas TDI-, IDI- and especially MDI-functionalized lignin-based oleogels displayed weak gel-like, or even a liquid-like, behaviors as a consequence of the respective chemical structures, which guide to higher steric hindrance, diminishing the formation of urethane linkages and/or Van der Waals forces. In general, oleogels exhibited an internal curing process due to the progressive formation of urethane linkages, which is closely related to the evolving rheological properties. The kinetics of this curing process was studied and an empirical model has been proposed to predict the evolution of the rheological properties with time., This work is a part of two research projects (CTQ2014-56038-C3-1R and TEP-1499) sponsored by the MINECO-FEDER and Junta de Andalucía programmes, respectively.

The tomato Mi-1 gene mediates plant resistance to whitefly Bemisia tabaci, nematodes, and aphids. Other genes are also required for this resistance, and a model of interaction between the proteins encoded by these genes was proposed. Microarray analyses were used previously to identify genes involved in plant resistance to pests or pathogens, but scarcely in resistance to insects. In the present work, the GeneChip™ Tomato Genome Array (Affymetrix®) was used to compare the transcriptional profiles of Motelle (bearing Mi-1) and Moneymaker (lacking Mi-1) cultivars, both before and after B. tabaci infestation. Ten transcripts were expressed at least twofold in uninfested Motelle than in Moneymaker, while other eight were expressed half or less. After whitefly infestation, differences between cultivars increased to 14 transcripts expressed more in Motelle than in Moneymaker and 14 transcripts less expressed. Half of these transcripts showed no differential expression before infestation. These results show the baseline differences in the tomato transcriptomic profile associated with the presence or absence of the Mi-1 gene and provide us with valuable information on candidate genes to intervene in either compatible or incompatible tomato-whitefly interactions.

16 pages, 7 figures, 3 tables, The morphology, molecular phylogeny and toxinology of two Coolia and one Prorocentrum dinoflagellate strains from Brazil were characterized. They matched with Coolia malayensis and Coolia tropicalis morphotypes, while the Prorocentrum strain fitted well with the morphology of Prorocentrum emarginatum. Complementary identification by molecular analyses was carried out based on LSU and ITS-5.8S rDNA. Phylogenetic analyses of Coolia strains (D1/D2 region, LSU rDNA), showed that C. malayensis (strain UFBA044) segregated together with sequences of this species from other parts of the world, but diverged earlier in a separate branch to sequences from São Paulo (Brazil) or Caribbean areas. Coolia tropicalis (strain UFBA055) grouped with other sequences of this species, in a subclade with an isolate from Belize, closer to a subgroup including isolates from Thailand, Australia and Hong Kong. Phylogenetic analyses (ITS-5.8S rDNA) of P. emarginatum (strain UFBA033) grouped together with another sequence of this species from China Sea. Diarrhetic shellfish poisoning toxins (OA, DTXs and PTX2) were not detected in P. emarginatum by mass spectrometry analyses. However, hemolytic assays in P. emarginatum and both Coolia strains in this study showed positive results, This study was funded by projects FAPESB – RED0006/2012 and CNPq (Productivity Scholarship in Research # 07368/2015-7), which were granted to J.M.C. Nunes; another CNPq grant (# 471303/2013-5) was granted to M. Menezes; the scholarships from CAPES (PhD scholarship # 9947-14-14-0/2014) and FAPESB (PhD scholarship Bol # 10685/2013) were granted to M.C.Q. Mendes

This work addresses the reuse of waste products as a raw material for lime putties, which are one of the components of mortar. 1:3 Lime/sand mortars very similar to conventional construction mortars were prepared using a lime putty obtained from the treatment of phosphogypsum with sodium hydroxide. The physical, rheological and mechanical properties of this phosphogypsum-derived mortar have been studied, as well as the mineralogical composition, microstructure by scanning electron microscope (SEM) and curing process by monitoring carbonation and ultrasonic propagation velocity. Considering the negative influence of sulphates on the hardened material, the behaviour of the material after sulphates precipitation by adding barium sulphate was additionally tested. Carbonation progressed from the outside to the inside of the specimen through the porous system by Liesegang rings patterns for mortars with soluble sulphates, while the carbonation with precipitated sulphates was controlled by diffusion-precipitation. Overall, the negative influence of low-sulphate contents on the mechanical properties of mortars was verified. It must be highlighted the importance of their precipitation to obtain adequate performance., This research was funded by Programa Estatal I+D+i Retos de la Sociedad of the Ministry of Science and Innovation (Spain), which supported this research (MAT2017-84228-R research project).

Vibrio s include several pathogenic bacteria that occur in aquatic environments. The presence of Vibrio has been assessed in many ecosystems by culture-based techniques. However, little is known on the contribution of Vibrio s in the sea, especially in areas subject to harmful algal blooms. A preliminary study in Sant Andreu de Llavaneres beach (NW Mediterranean) showed the presence of some Vibrio species during a recurrent bloom of the harmful benthic dinoflagellate Ostreopsis cf. ovata . In order to establish the importance of Vibrio s in a coastal area of the NW Mediterranean and to study the association with the dinoflagellate, we conducted a sampling monitoring for one year to quantify the concentration of Vibrio s both in the water (free-living and attached to particles) and in the epiphytic community of macroalgae. The aims were 1) to evaluate the relative abundance of Vibrio in the epiphytic and in the planktonic bacterial community, 2) to assess the percentage of free-living and attached Vibrio s in the planktonic community, and 3) to determine whether the presence of Vibrio s is associated with the blooms of the toxic dinoflagellate Ostreopsis or with other environmental parameters. For this purpose, a CARD-FISH molecular probe was applied for the specific detection of bacteria belonging to the genus Vibrio . Cells were quantified and the abundance of both particles and bacteria attached to particles were assessed. The maximum Vibrio concentration (1.3x104 cells ml –1 and 1.4x10 6 cells g –1 FW, for planktonic and epiphytic samples, respectively) was detected in September. Free-living Vibrio s contributed 0.38±0.24% to the total free-living planktonic community and 1.12±0.28% to the epiphytic bacterial community. However, their contribution was particularly high in the planktonic community attached to particles (17.37±20.49%). Although in the planktonic community Vibrio was found preferentially free-living (82.63±20.01%), particles are a niche for Vibrio s, since in particles Vibrio s may represent up to 72% of the total attached bacterial community. Abundance of planktonic Vibrio was correlated with Ostreopsis concentration and it is likely that they play a role in the wound infections suffered by beach users during the bloom.

It is well known that spontaneous oxidation is one of the main drawbacks for the industrial use of eco-friendly vegetable oil-based lubricants. Herein a quick and easy synthesis of different molecules belonging to stilbene family is reported, which together with a number of representative natural sources-derived products with antioxidant (AO) capacity have been tested as additives for improving the oxidative stability of a selected bio-lubricating grease formulation. Thus, different gel-like dispersions based on N-acylated chitosan in castor oil also including these additives have been prepared. Gel-like dispersions were characterized through thermogravimetric analysis (TGA), oxidation onset temperature (OOT) and small-amplitude oscillatory shear (SAOS) rheological measurements. These preliminary results demonstrate that, in general, these antioxidants delay N-acylated chitosan-based gel-like dispersions oxidation. However, the AO activity is more relevant in the case of propyl gallate and ascorbic acid palmitate and not so important in the family of stilbene derivatives. On the other hand, the addition of any antioxidant does not qualitatively affect the rheological response but unexpectedly may significantly modify the values of the SAOS functions. Remarkably, the delay of oxidation reactions occurs by exclusively employing natural resources-derived components, being these formulations environmentally acceptable as a whole and potentially employed in specific industrial applications.

This work has been focused on the preparation and characterization of gel-like dispersions based on sepiolite and castor oil potentially suitable as eco-friendly lubricating greases. Particularity, the effect of sepiolite content exerted on rheological, chemical, thermal and tribological properties was studied. The system exhibited a gel-like behaviour for all the concentrations considered (20–40 wt%) related to the development of a sepiolite three-dimensional colloidal network due to its characteristic nanoscale structure formed by fibers, laths and bundles. The values of both apparent viscosity and viscoelastic functions in the linear viscoelastic region increased with sepiolite content, as a consequence of a strengthening of the gel network. An empirical correlation between viscoelastic modulus and sepiolite concentration was proposed. From tribological point of view, the friction coefficient values and wear marks obtained after the frictional tests became lower when sepiolite concentrations decrease. Gel-like dispersion formulated with 30 wt% sepiolite showed appropriate rheological and tribological behaviour to be used as biolubricating greases.

The frictional and wear properties of novel bio-based greases consisting of epoxide-functionalized alkali lignins (EALs) dispersions in castor oil were examined. EALs used as thickeners were obtained by chemical modification of alkali lignin (AL) with poly (ethylene glycol) diglycidyl ether (PEGDE). The thickener concentrations and epoxy indices used spanned the ranges 2.5–10 wt% and 0.28–0.79 mol/kg, respectively. The influence of both variables on friction and wear was studied. Comparing the frictional behaviour of the biogreases and the base oil revealed that the influence of the thickener on lubrication performance differed with temperature, load, and sliding velocity. The thickener effectively reduced friction and wear, but especially at low concentrations (5 wt% or lower) and high epoxy indices (up to 0.79 mol/kg).

The stability of the thickener microstructure in lubricating greases influences their ability to reduce friction and protect the lubricated surfaces in a tribological system. Shear-induced degradation of the thickener network in lubricating greases that occurs as a result of reduced particle interactions can be considered a process associated with exceeding a critical energy level, i.e. the activation energy. The aim of this experimental study was to investigate the relationship between the activation energy, which represents the amount of energy required to produce shear-induced structural degradation, and the extent of the structural degradation that occurs under different shearing conditions. To this end, rotational transient flow tests were carried out in a rheometer at varying temperatures (25–70 °C) and a constant shear rate to quantify the activation energy of six model greases. The model greases differed in the nature and concentration of the thickener used, and the activation energy was calculated by fitting the rheological energy density to the Arrhenius equation. The activation energy was found to depend on the nature and concentration of the thickener in the greases; higher thickener concentrations resulted in lower activation energies. In addition, oscillation amplitude sweep tests were performed to obtain information about the early stages of shear-induced structural degradation. Lower activation energies were found to result in an earlier onset of shear-induced structural degradation. Finally, correlations between the activation energy and structural degradation of the model greases under different shear situations were presented and discussed. This enhanced understanding of the shear-induced degradation will facilitate the improvement of the service life of lubricating greases.

The freeze-drying process is a combination of 2 equally important processes, freezing, and drying. In the past, the effort was mainly focused on optimizing the drying process without considering the possible effects of the freezing step. During freezing, a solution undergoes several physical changes, including a supercooling state. The degree of supercooling of a solution dictates the ice habit (size, number, and morphology) during freezing, which impacts the subsequent drying process, such as the resistance to water vapor flow. Therefore, heterogeneous degree of supercooling leads to heterogeneous ice habits and, in turn, to heterogeneous drying behavior. This poses significant challenges during freeze-drying process development, optimization, and scale up. Hence, controlling the degree of supercooling significantly improves freeze-drying process design. The aim of the current review is to gather existing information on the physicochemical phenomena involved in the freezing process and how these phenomena impact the subsequent drying step of the freeze-drying process. In addition, modification of the freezing process and different techniques used to actively control the degree of supercooling during freezing will be reviewed and discussed. Their impact on freeze-drying process performance will be also addressed.

Considerable efforts are currently being made by the academic community and industry, aiming to develop environmentally friendly lubricants with suitable technical features for their performance. In this context, lignin could be considered a promising candidate to be used as a bio-sourced thickening agent to formulate eco-friendly lubricating greases. In this work, alkali lignin (AL) was chemically modified with poly(ethylene glycol) diglycidyl ether (PEGDE). Afterwards, the epoxidized lignin was properly dispersed in castor oil (CO) in order to obtain an oleogel for lubricant applications. The epoxidized lignins were characterized by means of epoxy index determination, thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. The epoxide-functionalized lignin-based oleogels were analyzed from both rheological and tribological points of view. It was found that the viscosity, consistency and viscoelastic functions of these oleogels clearly increased with the epoxy index of the epoxide-modified lignin compound. Thermo-rheological characterization of these oleogels revealed a slight thermal dependence of the viscoelastic moduli below 100 &deg, C, but a significant softening above that critical temperature. In general, these oleogels showed low values of the friction coefficient under the mixed lubrication regime as compared to the neat castor oil.

Several di- or tri-functional epoxides were used to chemically modify an industrial grade cellulose pulp from Eucalyptus globulus in order to thicken castor oil by dispersing epoxidized cellulose pulp fibers, resulting gel-like formulations with potential applications as biolubricants. Rheological properties of these colloidal suspensions were evaluated by analysing the effects of epoxidation degree and the epoxide chemical structure. With this aim, epoxidized cellulose pulp samples were characterized by means of epoxy index determination, thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. It was found that linear viscoelastic functions, determined in small-amplitude oscillatory shear (SAOS), and viscosity values of epoxidized cellulose pulp gel-like dispersions decreased by increasing the epoxy index, whereas the shear-thinning character was dampened with the extension of epoxidation. Aromatic di-functional epoxides provide higher values of these rheological functions than aliphatic ones.

The scope of this study is to elucidate the physical mechanisms influencing the transient flow behavior of lubricating greases based on biogenic oleochemicals from a polarity point of view. This includes the mutually interacting influence of base oil polarity and thickening agents on the rheologically-measured mechanical structural degradation in transient shear flow. Due to the high temperature dependence of Keesom forces in the background of polar-active bond mechanisms, the analysis of the transient flow response as a function of temperature allows to attribute the observed influences to differences in base oil polarity. In general, clay-thickened greases show a greater tendency to be rheologically influenced by base oil polarities than soap-thickened lubricating greases.

Several commercially available cellulose derivatives differing in the type of substituent and substitution degree (α-cellulose, methyl cellulose, 2-hydroxyethyl cellulose, methyl 2-hydroxyethyl cellulose and cellulose acetate propionate) have been functionalized with 1,6-hexamethylene diisocyanate (HMDI) and subsequently dispersed in castor oil to obtain chemical oleogels, which can be proposed as lubricating grease formulations completely based on renewable resources. NCO-functionalized cellulose derivatives used as thickening agents and corresponding oleogels were characterized by means of Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Oleogels were also rheologically investigated and gel microstructure determined by atomic force microscope (AFM) observations. Dispersions of the different cellulosic derivatives analyzed provide oleogels with a wide variety of rheological properties, thermal stability and physical appearance. Cellulose derivatives used as thickeners exhibited a reduced thermal resistance after NCO-functionalization due to the inclusion of the HMDI segments in the cellulose structure. However, the resulting oleogels presented suitable thermal resistance. The different rheological responses obtained, from solid-like to weak gels, were found to be basically dependent on the balance between the non-polar and polar substituents molar ratio in the biopolymer structure and the size of these substituents. The presence of non-polar groups reduces cellulose polarity and, therefore, increases the affinity by the oil medium, whereas large substituents seem to hinder the development of the three-dimensional gel network. An empirical correlation between the storage modulus, G ′, and a power function of both the molar ratio [− R polar /− R non-polar ] in each monomer,− R being the different substituents of cellulosic derivatives evaluated, and the ratio of average molecular weight of all substituents to cellulose monomer molecular weight has been proposed to predict the rheological behavior of resulting oleogel formulations.

In this work, several lignocellulose pulps from different origins and/or submitted to different treatments were cross-linked with hexamethylene diisocyanate (HMDI) and further dispersed in castor oil in order to obtain gel-like formulations based on renewable resources, which can be potentially applicable as semisolid lubricants. The rheological and tribological properties attained as well as physical and mechanical stability were suitable to consider these gel-like dispersions as efficient alternatives to traditional lubricating greases. The rheological behavior was evaluated by means of both small-amplitude oscillatory shear tests (SAOS) and viscous flow measurements, at different temperatures. The HMDI/cellulose pulp weight ratio applied in the cross-linking reaction can be used to modify and modulate the consistency and the values of rheological functions of these gel-like dispersions. However, the rheological behavior is not qualitatively affected by the amount of HMDI used as coupling agent. The the...

The overall objective of this work was to study the effect of reprocessing cycles of isotactic polypropylene (PP) on the rheological behavior and microstructure of gel-like dispersions in mineral oil. PP was subjected to 10 reprocessing cycles and oleogel samples were further prepared by using the mixing rheometry technique and characterized from a rheological point of view and polarized light optical microscopy (PLOM). Recycled polymer samples were also characterized by means of rheological measurements, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) to evaluate the property changes induced by reprocessing. The values of different linear viscoelastic functions (elastic modulus and complex viscosity) of recycled PP decrease with the number of reprocessing cycles, which influences oleogel rheological response. An empirical exponential correlation between the storage modulus (G′) of PP samples and the plateau modulus ( G N o ) of oleogels has been proposed to predict the rheological behavior of oleogels. Results were explained considering the scission of PP chains induced by the thermomechanical reprocessing treatment applied.

Summary This work deals with the development and characterization of new formulations based on different types of acylated chitosan, obtained using different acylation protocols and acyl chlorides, which are able to generate stable gel-like dispersions in castor oil. These dispersions can be proposed as promising candidates to replace current non-biodegradable lubricating grease formulations. The biopolymers and gel-like dispersions were characterized through Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). In addition to this, small-amplitude oscillatory shear (SAOS) measurements were performed on gel-like dispersions. The resulting oleogels demonstrated suitable thermal resistance although the inclusion of acyl segments into the polymer structure reduces thermal stabilities. The values of the linear viscoelastic functions and their evolution with frequency for gel-like dispersions of chitosans N -acylated with decanoyl chloride or N - and O -acylated with palmitoyl chloride were very similar to those exhibited for non-biodegradable commercial greases. A significant decrease in the storage and loss moduli was detected as the carbon chain length in the acyl group decreases in both N -acylated and N - and O -acylated chitosans. Moreover, both moduli decrease when the acylation reaction time increases, as a result of a major chitosan acylation degree, which provides weaker gels.

New oleogel formulations based on high-oleic sunflower oil (HOSO) and ethylene vinyl acetate copolymer (EVA)/polypropylene (PP) blends were prepared using the mixing rheometry technique and further characterized. The effects of PP tacticity and EVA vinyl acetate (VAc) content on the rheological, morphological, and thermal behavior of derived oleogels were investigated. Differential scanning calorimetry (DSC) and polarized-light optical microscopy (PLOM) observations indicated that VAc segments markedly influence the crystalline structure of polymeric fractions and phase morphology of oleogels. The normalized crystallinity of isotactic polypropylene (iPP) phase increased linearly with its concentration whereas syndiotactic polypropylene (sPP) content does not exert a significant influence. PLOM observations showed that VAc content plays an important role in the phase morphology of PP frictions (size and shape of crystals). The viscoelastic response of oleogels depended on PP tacticity and VAc content, which may be explained attending to the different microstructures attained. POLYM. ENG. SCI., 55:1429–1440, 2015. © 2015 Society of Plastics Engineers

This paper reports a physical characterization of multiple emulsions formulated with a green solvent (2-ethylhexyl lactate) and different HLB amphiphilic block copolymers (Atlas™ G-5000 and Atlox™ 4912), as emulsifiers. 15 wt% 2-ethylhexyl lactate emulsions stabilized by a 1:1 mass ratio of both copolymers were prepared with different copolymer concentrations in one single emulsification step, using a rotor-stator emulsification device. Multiple emulsions were characterized by means of electrolytic conductivity measurements, viscosity, optical microscopy, laser diffraction and multiple light scattering techniques. W/O/W emulsions were obtained in all cases, regardless of the copolymer composition used. All emulsions showed Newtonian behaviour and relatively low viscosity values (2–2.6 times the viscosity of water at 20 °C). Viscosity hardly increased with the overall copolymer concentration. The mean Sauter diameter of O/W globules increased with copolymer concentration, while the evolution of the volumetric mean diameter depended on the occurrence of some recoalescence. The onset of different simultaneous destabilization mechanisms was detected by multiple light scattering. Even though creaming was the predominant destabilization mechanism, a separated layer of oil phase due to coalescence was also observed in most cases after a long aging time. The destabilization kinetics was slowed down by increasing the total copolymer concentration when both types of copolymers were used.

The overall objective of this work was to study the influence of vinyl acetate (VAc) content on the rheological properties and microstructure of polymer gels based on conventional and high-oleic sunflower vegetable oils and ethylene-vinyl acetate copolymer (EVA). The mechanical properties during gel preparation can be in situ monitored through the evolution of torque with processing time by using the mixing rheometry technique. Linear viscoelastic measurements, as well as differential scanning calorimetry (DSC) tests and morphological observations, were performed on the resulting gels. From the experimental results, it can be concluded that VAc content and melt flow index of the EVA copolymer significantly affect the rheological and thermal responses of polymer gels. VAc content, mainly affecting EVA degree of crystallinity, and melt flow index influence the linear viscoelastic behaviour in opposite directions. On the contrary, the extension of the linear viscoelastic regime and gel-like to liquid-like response transition temperatures are mainly dominated by EVA degree of crystallinity, as confirmed through calorimetry tests and microscopy observations. The different fatty acid profile in sunflower oils tested does not exert an important influence on process rheokinetics and rheological behaviour.